1. Amines (McM chapt 24) pKa Alkylamines: ca 9-11 Arylamines: ca 4-5 (anilines)

2. Synthesis (McM 24.6) From KJ101 / KJM1010+1020: Alkylation (ammonia or amine, phtalimide) Reductive amination

3. Reductions

4. Synthesis (McM 24.6): “New” reactions Hofmann rearrangement

5. Curtius rearrangement

6. Reactions of amines (Alkylamines) (McM 24.7) Alkylamines: Alkylation (McM 24.7) Acylation (McM 21.4, 21.5) Hofmann elimination (≠ Hofmann rearrangement) E2 elimination to form alkene X= halogen, (OH) X ≠ NR 2 Strong base / bad leaving group

7. Morphine Codeine Removal of less sterically hindered H Not necessarily most stable alkene formed

8. Reactions of Arylamines (aniline derivatives) (McM 24.8) Weak base (pKa ca 4.6) Highly Activated for E-fil Ar Subst (o/p) Protect. as amide: Less activated, still o/p Nucleophilic Aromatic Substitution - Mechanisms S N Ar √ S N 1 Benzyne √ SRN1: Involves radicals (VNS: Vicarious Nucl. Subst.)

9. Formation of Diazonium Salts and the Sandmeyer Reaction N 2 as leaving group Cu-salt mediated react. Sandmeyer react. (radical mech.)

10. Diazo coupling Antibacterial sulfonamides